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Significant substitution effects in dipolar and non-dipolar supercritical fluids
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10.1063/1.3602159
/content/aip/journal/jcp/134/23/10.1063/1.3602159
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/23/10.1063/1.3602159

Figures

Image of FIG. 1.
FIG. 1.

Vibrational frequency shifts measured in all supercritical fluid systems at ρ r = 0.7. Left column: solute, measured band, and solvent. Cited references and measured temperatures are listed in Table I. Str: stretching mode, def: deforming mode, c-: cis-, t-: trans-, pNA: p-nitroaniline, MeOH: methanol, EtOH: ethanol, and p-ABN: p-aminobenzonitrile.

Image of FIG. 2.
FIG. 2.

Thermodynamic states for Raman spectral measurements on (a)–(f) pressure-temperature and (g)–(l) density-pressure phase diagrams. Solid lines in Figs. (a)-(f) are the liquid-vapor coexistence curves. Solid lines in Figs. (g)–(l) are visual guides obtained by fitting polynomial functions to the data. The term ρ r is the reduced density represented by ρ r = ρ/ρ c.

Image of FIG. 3.
FIG. 3.

(a) Typical example of Raman spectra of trans-stilbene in supercritical fluid. The band at around 1640 cm−1 has been assigned to the C=C stretching mode (see Ref. 5). (b, c) Density dependences of C=C stretching modes of trans-stilbene in (b) scCHF3 and (c) scCO2. Solid lines are the curve fits using the Lorentzian functions. The term ρ r is the reduced density represented by ρ r = ρ/ρ c. In the manuscript, we obtained the peak frequencies of C=C stretching modes by analyzing the spectra using Lorentzian functions.

Image of FIG. 4.
FIG. 4.

Frequency shifts of C=C stretching modes of trans-stilbene (red), cis-stilbene (Ref. 10) (pink), and cis-C2H2Cl2 (Ref. 11) (black) in scCHF3 at T r = 1.02. Solid lines are visual guides obtained by fitting polynomial functions to the data.

Image of FIG. 5.
FIG. 5.

(a, b) Repulsive (green), net (black), and attractive (red) shifts of C=C stretching modes of trans-stilbene in (a) scCHF3 and (b) scCO2 at T r = 1.02. (c, d) Attractive shift of trans-stilbene (closed circle), cis-stilbene (open circle), and cis-C2H2Cl2 (+) in (c) scCHF3 and (d) scCO2. Solid lines are visual guides obtained by fitting the polynomial functions to the data.

Image of FIG. 6.
FIG. 6.

(a) The method to obtain the local density augmentation, (ρ localρ)/ρ c. Symbols are experimental attractive shifts. Solid line is linear line based on the mean field approximation. (b, c) Local density augmentations of (b) cis-stilbene and (c) trans-stilbene in scCO2. The quantity of ρ r is expressed as ρ r = ρ/ρ c. Solid lines are visual guides obtained by fitting polynomial functions to the data.

Image of FIG. 7.
FIG. 7.

Attractive shifts of C=C stretching modes of (a) trans-stilbene and (b) cis-stilbene (Ref. 10) in scCHF3 (blue) and scCO2 (red) at T r = 1.02.

Tables

Generic image for table
Table I.

Systems, temperatures, and references of the data in Fig. 1. The number in the left column represents the order of the shifted amount at ρ r = ρ/ρ c = 0.7, as shown in Fig. 1.

Generic image for table
Table II.

Molecular parameters for calculations of the repulsive shifts.

Generic image for table
Table III.

Molecular parameters.

Generic image for table
Table IV.

Dispersion (dis), dipole-induced-dipole (DID), and dipole-dipole terms in Ref. 44.

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/content/aip/journal/jcp/134/23/10.1063/1.3602159
2011-06-21
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Significant substitution effects in dipolar and non-dipolar supercritical fluids
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/23/10.1063/1.3602159
10.1063/1.3602159
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